Quenching oil composition and method of quenching metal

ABSTRACT

An improved quenching oil composition comprising a major amount of a quench oil of lubricating viscosity; a minor amount of at least one carbon linked poly-phenate metal compound sufficient to improve the anti-staining properties of the composition and at least one naphthyl amine sufficient to improve the resistance to oxidation of the composition. The compositions may also include a minor amount of at least one of certain diamine components to provide further improved oxidation resistance. An improved method for quenching is also disclosed.

United States Patent 1191 De Vries et al.

[451 Dec. 17, 1974 QUENCHING OIL COMPOSITION AND METHOD OF QUENCHING METAL [75] Inventors: Donald L. De Vries, South Holland;

Barnard C. Creech, Homewood, both of 111.

[73] Assignee: Atlantic Richfield Company, Los Angeles, Calif.

[22] Filed: June 25, 1973 21 App1.No.:373,530

[52] US. Cl 148/28, 148/29, 252/77 [51] Int. Cl B23k 35/24 [58] Field Of Search 148/28, 12.1, 25, 27, 29,

[56] References Cited UNITED STATES PATENTS 2,736,701 2/1956 Neff 252/32.7 3,159,510 12/1964 Rozalsky et 3,281,288 10/1966 Carver et al. 148/206 3,498,850 3/1970 Morton 148/29 FOREIGN PATENTS OR APPLICATIONS 1,224,636 3/1971 Great Britain 148/28 Primary Examiner-Walter R. satterfield Attorney, Agent, or FirmFrank J. Uxa

[57] ABSTRACT An improved method for quenching is also disclosed.

19 Claims, N0 Drawings QUENCHING OIL COMPOSITION AND METHOD OF QUENCHING METAL The present invention relates to improved quenching oil compositions and methods for using same. More particularly, the present invention relates to quenching oil compositions having both improved anti-staining properties and improved resistance to oxidation, and to an improved method for quenching heated metals.

Quenching oil compositions used, for example, to quench heated metals, must provide efficient cooling without detrimentally affecting the metal being quenched. Certain prior art quenching oil compositions have shown a tendency to cause stains to be formed on the metal. These stains, at best, require additional processing to remove and may require that the metal be scrapped. Therefore, it would be advantageous to provide a quenching oil composition having improved antistaining properties.

Since quenching oil compositions are normally in use over a protracted period of time, they are subject to deterioration by oxidation. Therefore, it would be advantageous to provide a quenching oil composition having improved resistance to oxidation.

Therefore, one of the primary objects of the present invention is to provide a quenching oil composition having improved anti-staining properties.

Another object of the present invention is to provide a quenching oil composition having improved resistance toward oxidation.

An additional object of the present invention is to provide an improved method of quenching heated metal. Other objects and advantages of the present invention will become apparent hereinafter.

An improved quenching oil composition has now been discovered which comprises a major amount of quench oil of lubricating viscosity having a minimum flash point of at least about 250F., a minor amount sufficient to improve the anti-staining properties of the composition of at least one metal phenate compound of a phenolic component having the following structure OII on on I i 1 l IR ly-@+R' R' I s l j R Ron I 3 wherein R is selected from the group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing up to about 5 carbon atoms and mixtures thereof, n is an integer from zero to about 6, prefwherein R is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals containing from 1 to about 30, preferably from about 6 to about 18, carbon atoms, a is an integer from zero to 7, preferably zero to l inclusive and D is a monovalent hydrocarbon radical containing from 1 to about 30, preferably from about 1 to about 18 carbon atoms.

In a preferred embodiment of the present invention the quenching oil compositions further comprise a minor amount sufficient to further improve the resistance to oxidation of the composition of at least one diamine component having the fOllOWino emwherein R R R and R areindependently selected from the group consisting of hydrogen, alkyl having from 1 to about 12 carbon atoms, and aryl, aralkyl, alkaryl having from 6 to about 22 carbon atoms, and B is selected from the group consisting of divalent aromatic-containing hydrocarbon radicals and substituted divalent aromatic-containing hydrocarbon radicals containing from 6 to about 30, preferably from about 6 to about 24 carbon atoms.

Of course, combinations or mixtures of two or more metal phenate compounds, naphthyl amines and diamine components may be used in a single quenching oil composition and, therefore, such mixtures are within the scope of the present invention.

The quench oil of lubricating viscosity used in the present invention may be eithernaturally occurring or synthetically made. It may be animal, vegetable or minera] in character, with mineral oils being preferred. However, because of the relatively high temperatures of many quenching operations, the oil should have a minimum flash point of at least about 250F. and preferably in the range from about 250F. to about 500F., or higher. Typical examples of suitable lubricating oils include those having a viscosity in the range from about 50 SUS to about 1000 SUS, preferably from about 50 SUS to about 300 SUS, at 100F. These oils may be refined or otherwise processed to produce the desired quality. Petroleum oils are especially preferred. A specific example of the quench oil used in the present compositions is a petroleum derived oil mixture having a viscosity of about 200 SUS at 100F. Combinations or mixtures of two or more such quenching oils in a single quenching composition are often used to provide the desired physical properties and these mixtures are, therefore, within the scope of the invention. The quench oil comprises ,a major amount, preferably at least about and more preferably at least about by weight of the total composition.

Many conventional additives which are known to increase the initial rate, and therefore, the overall rate, of cooling of quenching oil compositions may be included in the quench oils. To illustrate, heavy mineral oil fractions, e.g., petroleum resins, having minimum flash points in the range from about 400F. to about 700F. and viscosities in the range from about 200 SUS to about 2000 SUS at 210F. are suitable for use in these quench oils. Although it is preferred that this additive be of naturally occurring mineral oil origin, e.g., such as the petroleum resins noted above, various synthetic materials, such as olefin polymers, also are suitable. Typically, these additives comprise from about 0.5 to about 20%, preferably from about i to about by weight of the quench oil.

The metal phenate compounds useful in the quenching oil compositions of the present invention are preferably oil-soluble. The metals which may be used to form the metal phenate compounds suitable for the present compositions include the alkaline earth metals such as barium, calcium, strontium, and magnesium; the alkali metals such as sodium, potassium and lithium; and polyvalent metals such as lead, tin, zinc, aluminum, copper, mercury, vanadium, chromium, molybdenum, manganese, iron, cobalt and nickel. The alkali and, particularly, the alkaline earth metals are preferred. The most preferred metal for use in the phenate compounds is calcium. Typically, these metal phenate compounds comprise from about 0.1 to about preferably from about 0.5 to about 8%, by weight of the total quenching oil composition.

The metal phenate compounds useful in the present invention may. be referred to as carbon linked polyphenate metal compounds. Although the carbon link between phenyl groups can contain as many as about 5 carbon atoms, it is preferred that this carbon link contain only one carbon atom.

It is preferred that the phenolic component comprise the following structure on on l I l l g R R n R wherein each R, R and R and n are as previously defined. The monovalent essentially hydrocarbon radicals from which each R is independently selected include alkyl and alkenyl groups containing from about 3 to about 20, preferably from about 8 to about 20, carbon atoms; aryl, aralkyl, alkaryl, aryl alkenyl and alkenyl aryl groups containing from about 6 to about 20, preferably from about 8 to about carbon atoms. The divalent essentially hydrocarbon radicals from which each R is independently selected include alkylene groups containing from l to about 5 carbon atoms.

Typical examples of suitable alkyl groups include propyl, butyl, pentyl, octyl, decyl, dodecyl, tetradecyl, stearyl and the like. Suitable alkenyl groups include propenyl, butenyl, pentenyl, octenyl, decenyl, dodecenyl, tetradecenyl, oleic and the like. Suitable aryl, aralkyl, alkaryl, aryl alkenyl and alkenyl aryl groups include phenyl, naphthyl, phenyl ethyl, phenyl hexyl, phenyl octyl, phenyl tetradecyl, naphthyl hexyl, naphthyl octyl, ethyl phenyl, hexyl phenyl, octyl phenyl, tetradecyl phenyl, hexyl naphthyl, octyl naphthyl, phenyl ethenyl, phenyl hexenyl, phenyl octenyl, phenyl tetradecenyl, naphthyl hexenyl, naphthyl octenyl, ethenyl phenyl, hexenyl phenyl, octenyl phenyl, tetradecenyl phenyl, hexenyl naphthyl, octenyl naphthyl and the like. Included among the suitable alkylene groups are methylene, ethylene, propylene, butylene, pentylene and the like.

The above-described essentially hydrocarbon radicals may include non-hydrocarbonaceous substituents thus forming substituted monovalent and divalent essentially hydrocarbon radicals. Suitable substituents include those which do not materially interfere with the effectiveness, e.g., anti-staining properties, of the metal phenate compound. Typical examples of such noninterferring substituents include OH,

halide andthe like radicals.

It is preferred that each R be an alkyl group, more preferably the same alkyl group, containing from about 8 to about 20 carbon atoms, and that each R contain 1 carbon atom. At least one R may contain a carbonyl carbon atom or itself be a carbonyl group. The carbony] functionality can result from oxidation of a hydrocarbon radical R. For example, if R' is methylene, oxidation willproduce a carbonyl group.

In addition, at least one of the terminal phenyl groups of the metal phenate compound may be further substituted with non-interferring radicals, both monovalent essentially hydrocarbon radicals containing from about 8 to about 20 carbon atoms and non-hydrocarbon radicals, i.e., radicals which do not materially interfere with the effectiveness of the phenate compound in the compositions of the present invention. Groups including, for example, R and non-hydrocarbon radicals such as OH,

halide and the like radicals, may be substituted on the terminal phenyl groups. In addition, a radical selected from the group consisting of may form at least part of a substituent on at least one of the terminal phenyl groups.

The carbon linked poly-phenate metal compounds suitable for use in the present invention may be prepared by conventional procedures well known in the art, for example, as disclosed in US. Pat. No. 2,736,701. These phenate metal compounds can be prepared by condensing an alkylated phenol with a low molecular weight aldehyde, preferably formaldehyde, in the presence of a basic compound, e.g., hydroxide, of the desired metal. This basic compound may act both to catalyze the condensation, although other condensation catalysts such as sulfuric acid and other strong mineral acids may be used, and to react with the phenolic hydroxy groups to form the desired polyphenate metal compound. The condensation may be catalyzed by one basic compound and the phenolic hydroxy groups reacted with a different basic compound. However, it is preferred to use the same basic compound to perform both functions. It may be necessary to add additional basic compound after the condensation has stopped in order to form the desired metal phenate compound. The condensation and phenolic hydroxy group reaction conditions are well known in the art.

The naphthyl amines suitable for use in the present invention comprise a broad class of compounds. The general structural formula for these compounds is as follows R N H wherein R is selected from the group consisting of hydrogen and monovalent hydrocarbon radicals containing from I to about 30, preferably from about 6 to about 18 carbon atoms, a is an integer from zero to 7, preferably zero to l inclusive, D is a monovalent hydrocarbon radical containing from I to about 30, preferably from about 1 to about 18 carbon atoms. Included among the monovalent hydrocarbon radicals contemplated by the present invention are, for example, alkyl, aryl, aralkyl, alkaryl and substituted counterparts of these radicals. Included among the suitable amines are phenyl alphaor betanaphthylamine, octylphenyl alphaor betanaphthylamine, alpha-alpha, alpha-beta or beta-beta dinaphthylamines, various phenanthrylanthyrl-naphthylamines, xylyl naphthylamines, dodecyl phenyl naphthylamines, biphenyl naphthylamines and phenyl naphthylamines alkylated with olefins containing from about 8 to 24 carbon atoms per molecule. Specific examples of these olefins include pinene, a-methylstyrene, and the like. The naphthylamines in which R is a radical selected from the group consisting of aryl and alkaryl containing from 6 to about 18 carbon atoms, especially phenyl alpha naphthylamine, are of particular usefulness in the present invention and are, therefore, the more preferred class of compounds for use in the present invention. The naphthylamines often comprise from about 0.01% to about 5%, preferably from about 0.1% to about 2%, by weight of the total quenching oil composition. i

In choosing the diamine component, it is preferred that R and R be H, i.e., hydrogen. Examples of the alkyl groups from which R, R R and R may be selected include methyl, ethyl, isopropyl, sec-butyl, cyclohexyl, octyl, nonyl, decyl and the like. Examples of the aryl, aralkyl and alkaryl groups from which R R R and R may be selected include phenyl, benzyl, phenyl ethyl, phenyl isopropyl, phenyl octyl, phenyl decyl, tolyl, isopropyl phenyl, octyl phenyl, decyl phenyl and the like. Examples of the divalent aromatic-containing hydrocarbon radicals from which B may be selected, include phenylene, alkylene diphenylene and phenylene dialkylene wherein the alkylene groups contain from 1 to about 12 carbon atoms, and the like radicals. These divalent hydrocarbon radicals may be substituted with minor amounts of essentially noninterferring oxygen, sulfur and the like. Examples of the suitable substituted divalent aromatic-containing hydrocarbon radicals include divalent diphenyl ethers, and diphenyl sulfides and the like. When the diamine components are included in the compositions of the present invention, they often comprise from about 0.01% to about 5%, preferably from about 0.05% to about 2%, by weight of the total quenching oil composition.

Because of their outstanding performance in the compositions of the present invention, the following diamine components are among those preferred: Bis-(N- sec-butyl-p-amino phenyl) methane; N-isopropyl-N'- phenyl-p-phenylene diamine; N-cyclohexyl-N-phenylp-phenylene diamine; 2,2-Bis-(p-N,N- dimethylaminophenyl) propane and mixtures thereof.

In addition to the additives already described, the quenching oil compositions of the present invention may contain other agents such as antifoam agents, corrosion inhibitors, etc.

The compositions of the present invention are particularly useful in a method of quenching heated metal which comprises contacting the heated metal with such composition at conditions to cool the metal. Prior to such contacting the metal is heated to an elevated temperature, e.g., from about 1000F. to about 2500F. During the course of such contacting, the heated metal is preferably immersed in the quenching oil composition. Metals, such as carbon steel, which require quenching during, for example, manufacture and/or fabrication, may be treated using the present method.

The following examples illustrate more clearly the process of the present invention. However, these illustrations are not to be interpreted as specific limitations on the invention.

EXAMPLES 1 and 2 These examples illustrate certain of the advantages of the present invention.

Two compositions were blended at slightly elevated temperatures, i.e., from about F. to about l30F., to insure proper mixing. These compositions were as follows:

A commercially available mixture of about 50% by weight of active material in a mineral oil carrier. This carbon bridged calcium phenate compound is derived from the condensation of alkyl phenol with formaldehyde. The material contained 2.4% by weight of calcium. Infra-red spectrometry indicates the phenatc salt contains carbonyl functionality which may be located at either or both a carbon bridge or as part of a substituent on a terminal phenyl group. Based upon molecular weight considerations and elemental analysis, the phenate compound comprises 6 aromatic nuculi with single carbon atom bridges in between.

"A mixture of about 50% by weight of active material in a mineral oil carrier. The active material comprises mono-sulflde linked calcium phenate compound derived from dodecyl phenol.

These two compositions were tested using a laboratory staining test which is known to give a reasonable comparative correlation with staining properties of such compositions in actual quenching operation.

The staining test used involves passing air through a 3000 cc. quantity of the oil composition being tested. The oil is contained in an open steel beaker and is subjected to constant stirring. The oil is heated to and maintained at 350F. using a chrome immersion heater. Air is bubbled through the oil at a rate of 0.1 cu.ft./ hour using a sintered glass dispersing tip. The tendency for varnish and/or carbonaceous formation on the 5 heater is periodically observed. The longer the time before deposits form, the better the anti-staining properties of the oil composition. Also, physical tests on the oil at approximately 100 hour intervals are made by re- The oxidation test used involves passing air through a 150 cc. sample of the oil composition being tested. The composition is placed in a glass flask equipped with a reflux condenser. The oil is heated to and maintained at 342F. using an external heating source. Air is bubbled into the oil at the rate of 10 liters/hour for 175 hours. After this period, various physical tests are carried out on the used oil composition to determine the degree of oxidation.

moving 200 cc. of oil. An equivalent amount of oil is 10 Results of these Physic?!l tests are as fol-IOWSI COMPOSlTlON l 3 4 5 6 7 Property Viscusit SUS at 100F.

New i1 259 256 258 255 260 261 Used Oil 893 451 859 333 843 960 Viscosity increase, "In 245 76 232 31 224 267 Acid Number, (ASTM Saponification Number (ASTM D-94) 50.2 20.8 53.3 11.2 35.6 53.4

n-Pentane insolubles,

Wt.% of Used Oil 4.57 2.21 3.14 1.28 3.97 4.58

Benzene lnsolubles,

Wt.% of Used Oil 0.19 0.49 0.16 0.47 0.41 0.03

Insoluble Resins,

Wt.% of Used Oil 438 1.72 2.98 0.81 3.56 4.55

added to the beaker to replace the material removed 3 for these physical tests.

Results of the staining tests are as follows:

COMPOSlTlON HOURS TO HEATER VARNlSH These results indicate that quenching oil compositions containing carbon linked poly-phenate metal compounds have improved anti-staining properties.

EXAMPLES 3 to 7 These examples illustrate the improved resistance to oxidation of the present compositions.

Four additional compositions were blended at 45 slightly elevated temperatures. These compositions, along with Composition 1, are as follows:

In addition, Composition 5, which includes both phenyl-a-naphthylamine and 4,4'-methylene-bis-N- sec-butylaniline, possesses superior oxidation resistance. This is particularly suprising in view of the fact that 4,4-methylene-bis-N-sec-butyl-aniline alone,

COMPOSITION l 3 4 5 6 7 Weight Percent Component Mineral Oil. 200 SUS Petroleum Resin, 1000 SUS at 210F. 5.0 5.0 5.0 5.0 5.0 5.0

Carbon Linked Poly Phenate Metal I Compound i 2.0 2.0 2.0 2.0 2.0 2.0

Phenyl-a-Naphthylamine 0.5 0.5

Bis-(Nsec-butyl-pamino phenyl) methane 0.2 0.2

4,4'-methylene-bis- 2,4-di-ten-butylphenol 0.5

4,4'isopropylidene-bis N-sec-butylaniline 0.5

*See Example 1 for description of component.

Composition 4, provides little or no oxidation resistance.

Clearly, the present quenching oil compositions which contain both a carbon linked poly-phenate metal compound and a naphthylamine have unexpectedly improved anti-stain properties and oxidation resistance.

EXAMPLES 8 and 9 These examples illustrate the use of the quenching oil compositions of the present invention.

Compounded oils having the same chemical compositions as Compositions 3 and are employed to rapidly cool carbon steel from a temperature of about 1650F. The carbon steel to be cooled is brought into contact with the compounded oil by immersing the steel in the oil. It is found that both compounded oils are effective to rapidly cool the carbon steel.

While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows.

1. A quenching oil composition comprising a major amount of quench oil of lubricating viscosity having a minimum flash point of at least about 250F.', a minor amount sufficient to improve the anti-staining properties of said composition of at least one metal phenate compound of a phenolic component having the following structure an (|)H an l 1 11? l R -EX R l [WIT \XR l (R)X.l R

wherein each R is independently selected from the group consisting of monovalent essentially hydrocarbon radicals containing from about 3 to about 20 carbon atoms, each R is independently selected from the group consisting of divalent essentially hydrocarbon radicals containing from 1 to 5 carbon atoms and a carbonyl group, each R is independently selected from the group consisting of non-interferring hydrocarbon radicals containing up to about 20 carbon atoms, noninterferring non-hydrocarbon radicals,

wherein R is selected from the group consisting of hydrogen and monovalent essentially hydrocarbon radicals containing up to about 5 carbon atoms and mixtures thereof, n is an integer from zero to about 6 and P, X and T are each integers from zero to 3; and a minor amount sufficient to improve the resistance to oxidation of said composition of at least one naphthyl amine having the following structure phenate compound is present in an amount from about 0.1% to about by weight of the total composition and said naphthyl amine is present in an amount from 10 about 0.01 to about 5% by weight of the total composition.

3. The composition of claim 2 wherein said metal phenate compound is a compound of a metal selected from the group consisting of alkali metal and alkaline 15 earth metal.

4. The composition of claim 3 wherein said metal phenate compound is a compound of an alkaline earth metal and each R is a radical independently selected from the group consisting of aryl and alkaryl containing from 6 to about 8 carbon atoms.

5. The composition of claim 4 wherein said metal phenate compound is a compound of calcium.

6. The composition of claim 5 wherein said phenolic component has the following structure:

[R2111 [R lT l R R n It 7. The composition of claim 3 wherein each R contains from about 8 to about 20 carbon atoms and each R contains 1 carbon atom.

8. The composition of claim 5 wherein each R contains from about 8 to about 20 carbon atoms, each R contains 1 carbon atom and said naphthyl amine is phenyl alpha naphthylamine.

9. The composition of claim 1 which further comprises a minor amount sufficient to further improve the resistance to oxidation of said composition of at least one diamine component having the following structure:

wherein R R R and R are independently selected from the group consisting of hydrogen, alkyl having from 1 to about 12 carbon atoms, and aryl, aralkyl, alkaryl having from 6 to about 22 carbon atoms, and B is selected from the group consisting of divalent aromatic-containing hydrocarbon radicals and substituted divalent aromatic-containing hydrocarbon radicals containing from 6 to about 30 carbon atoms.

10. The composition of claim 9 wherein said metal phenate compound is present in an amount from about 0.1% to about 15% by weight of the total composition and said naphthyl amine is present in an amount from about 0.01% to about 5% by weight of the total composition and said diamine component is present in an amount from about 0.01% to about 5% by weight of the total composition.

11. The composition of claim 10 wherein said metal phenate compound is a compound of an alkaline earth metal and each R is a radical independently selected from the group consisting of aryl and alkaryl containing from 6 to about 8 carbon atoms, R and R are hydrogen, and B contains from 6 to about 24 carbon atoms, 12. The composition of claim 11 wherein said metal phenate compound is a compound of calcium, said phenolic component has the following structure l l RI I I XjLMT l l H n R wherein each R contains from about 8 to about carbon atoms, each R contains 1 carbon atom and said naphthylamine is phenyl alpha naphthylamine and said diamine component is selected from the group consisting of Bis-(N-sec-butyl-p-amino phenyl)methane; N- isopropyl-N'-phenyl-p-phenylene diamine; N- cyclohexyl-N'-phenyl-p-phenylene diamine; 2,2-Bis(p- N,N-dimethylaminophenyl) propane and mixtures thereof.

13. in a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 1.

14. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 3.

15. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 5.

16. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 8.

17. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 9.

18. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 10.

19. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim 12.

Patent No. Dated December 17,1974

Inventor) Donald L. DeVries and Barnard C. Creech It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

At column 9;, lines 33 to 39; delete the structure OH OH and substitute Signed and sealed this 11th day of February 1975.

(SEAL) Attest:

RUTH C. MASON C. MARSHALL DANN testin Offi Commissioner .of Patents 

1. A QUENCHING OIL COMPOSITION COMPRISING A MAJOR AMOUNT OF QUENCH OIL OF LUBRICATING VISCOSITY HAVING A MINIMUM FLASH POINT OF AT LEAST ABOUT 250*F.M A MINOR AMOUNT SUFFICIENT TO IMPROVE THE ANTI-STAINING PROPERTIES OF SAID COMPOSITION OF AT LEAST ONE METAL PHENATE COMPOUND OF A PHENOLIC COMPONENT HAVING THE FOLLOWING STRUCTURE
 2. The composition of claim 1 wherein said metal phenate compound is present in an amount from about 0.1% to about 15% by weight of the total composition and said naphthyl amine is present in an amount from about 0.01 to about 5% by weight of the total composition.
 3. The composition of claim 2 wherein said metal phenate compound is a compound of a metal selected from the group consisting of alkali metal and alkaline earth metal.
 4. The composition of claim 3 wherein said metal phenate compound is a compound of an alkaline earth metal and each R4 is a radical independently selected from the group consisting of aryl and alkaryl containing from 6 to about 8 carbon atoms.
 5. The composition of claim 4 wherein said metal phenate compound is a compound of calcium.
 6. The composition of claim 5 wherein said phenolic component has the following structure:
 7. The composition of claim 3 wherein each R contains from about 8 to about 20 carbon atoms and each R'' contains 1 carbon atom.
 8. The composition of claim 5 wherein each R contains from about 8 to about 20 carbon atoms, each R'' contains 1 carbon atom and said naphthyl amine is phenyl alpha naphthylamine.
 9. The composition of claim 1 which further comprises a minor amount sufficient to further improve the resistance to oxidation of said composition of at least one diamine component having the following structure:
 10. The composition of claim 9 wherein said metal phenate compound is present in an amount from about 0.1% to about 15% by weight of the total composition and said naphthyl amine is present in an amount from about 0.01% to about 5% by weight of the total composition and said diamine component is present in an amount from about 0.01% to about 5% by weight of the total composition.
 11. The composition of claim 10 wherein said metal phenate compound is a compound of an alkaline earth metal and each R4 is a radical independently selected from the group consisting of aryl and alkaryl containing from 6 to about 8 carbon atoms, R5 and R6 are hydrogen, and B contains from 6 to about 24 carbon atoms.
 12. The composition of claim 11 wherein said metal phenate compound is a compound of calcium, said phenolic component has the following structure
 13. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 1. 14. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 3. 15. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 5. 16. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 8. 17. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil cOmposition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 9. 18. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 10. 19. In a method of quenching heated metal wherein heated metal is contacted with a quenching oil composition and said metal is cooled, the improvement which comprises contacting said heated metal with the composition of claim
 12. 